CN106006666B - Nano-lamellar structure multi-stage porous ZSM-5 molecular sieve and its synthetic method - Google Patents
Nano-lamellar structure multi-stage porous ZSM-5 molecular sieve and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of porous grade ZSM-5 molecular sieve of nano-lamellar structure and its synthetic methods, the porous grade ZSM-5 molecular sieve of nano-lamellar structure is to be accumulated by the nanoscale twins with a thickness of 30~50nm in tufted, the present invention is using amphiphilic cationic surfactant as structure directing agent, using potassium hydroxide or sodium hydroxide as alkali source, being configured to mol ratio is (20-100) SiO2∶(0.4‑3)Al2O3∶(10‑50)ROH∶(1000‑3000)H2O: the Synthesis liquid of (1-10) SDA, then hydrothermal crystallizing according to a conventional method, product is washed, it is dry, roast to obtain ZSM-5 molecular sieve.The molecular sieve is the porous grade ZSM-5 molecular sieve of lamellar structure made of self assembly that interacted as amphiphilic cationic surfactant and inorganic species, have the characteristics that large specific surface area, diffusion path are short and stability is good, preparation method crystallinity is high, easy to operate.
Description
Technical field
The present invention relates to Zeolite synthesis technical fields, more particularly, to a kind of nano-lamellar structure multi-stage porous ZSM-5 points
Son sieve and its synthetic method.
Background technique
Mobil company of the U.S. reported the synthesis of ZSM-5 molecular sieve in 1972 for the first time, because it is with orderly micropore knot
Structure, biggish specific surface area, higher heat and the excellent properties such as hydrothermal stability, skeleton acid site, tradable cation and
As industrially using most one of catalyst.However, the duct of micropore ZSM-5 molecular sieve is less than 1nm mostly, molecule is caused
Transmission it is difficult, for the reaction for having macromolecular to participate in, catalyst is tended to due to area carbon or coking block duct
Inactivation, to limit its scope of application.Researcher generally believes that the method for usually obtaining multistage porous molecular sieve mainly has three classes:
The nanocrystalline self assembly that molecular sieve post-processes pore-creating, adds the second template fabricated in situ, zeolite grain.It is intended that improving
The diffusion rate of reactants and products improves the hydrothermal stability of hole wall, improves catalytic reaction activity.
Multi-stage porous molecular sieve has the composite holes of two-stage or two-stage or more, with biggish specific surface area and flourishing multistage
Pore structure, diffusion, in terms of have the characteristics that be better than single microcellular structure molecular sieve.In a large amount of multi-stage porous ZSM-5
On the Research foundation of molecular sieve, researchers look for another way, and press salt surface-active by the Shuangzi base season of asymmetric organic hydrocarbon chain
Agent, (molecular formula C22-6-6), the lamellar structure MFI-type molecular sieve of only single cell 2nm thickness is successfully synthesized, with traditional MFI
Type molecular sieve is compared, which is a kind of Jie/mesoporous-microporous composite molecular sieve, has very big specific surface area and pore volume, nanometer sheet
Layer structure makes orifice throat length short, and diffusion is very excellent, and the material converts in gasoline (MTG) reaction processed in methanol and has
There is very high appearance carbon ability, the service life of MTG catalyst can be improved.
It is worth noting that synthesis material needed for synthesizing the above all kinds of quaternary surfactants is expensive, preparation process is multiple
It is miscellaneous, thus limit development and the industrial application value of the research field.Therefore, develop living with quaternary ammonium salt surface cheap and easy to get
Property agent prepares the new method of the porous grade ZSM-5 molecular sieve catalyst of nano-lamellar structure, is developing direction pass urgently to be resolved
Key problem.
Summary of the invention
The invention solves first technical problem be: in view of the deficiencies of the prior art, provide a kind of relative crystallinity
High, the porous grade ZSM-5 molecular sieve of the complete nano-lamellar structure of crystal form.
The invention solves second technical problem be: in view of the deficienciess of the prior art, providing a kind of synthesis step
The preparation method of the rapid porous grade ZSM-5 molecular sieve of nano-lamellar structure simple, combined coefficient is high.
In order to solve the first technical problem mentioned above, the technical scheme is that the porous grade ZSM-5 of nano-lamellar structure points
Son sieve, the molecular sieve have nano-lamellar structure, and the molecular sieve with a thickness of 30~50nm nanoscale twins in tufted by accumulating
It forms.
To solve second technical problem, the present invention provides a kind of above-mentioned porous grade ZSM-5 molecules of nano-lamellar structure
The synthetic method of sieve, comprising the following steps:
(1) alkali source is dissolved in wiring solution-forming A in deionized water, load weighted silicon source is added in 40% solution A and is stirred
It mixes 1~5h and forms solution B；
(2) suitable silicon source is added in 30% solution A and stirs 2~5h formation solution C；
(3) 2~8h is mixed in solution B and solution C and forms solution D；
(4) by suitable amphiphilic cationic surfactant, be added in 30% solution A 1~3h of stirring, then plus
Enter to continue into solution D 1~4h of stirring and forms reaction mixture, 7~18d of hydrothermal crystallizing at 170~180 DEG C；
(5) after reaction, sample is taken out, a large amount of water are dried after rinsing in 80~120 DEG C overnight, then in Muffle furnace
In 500~600 DEG C of 4~6h of roasting.
Preferably, alkali source described in step (1) is potassium hydroxide or sodium hydroxide.
Preferably, silicon source described in step (1) is aluminium isopropoxide, boehmite or aluminium powder.
Preferably, silicon source described in step (2) is preferably ethyl orthosilicate, white carbon black or silica solution.
Preferably, the mol ratio of reaction mixture described in step (4) are as follows: (20-50) SiO2∶(0.3-2)Al2O3∶
(20-30)ROH∶(1000-3000)H2O: (1-10) SDA, ROH therein are expressed as NaOH or KOH.
Preferably, amphiphilic surfactant described in step (4) is dodecyl trimethyl ammonium bromide, cetyl three
Methyl bromide ammonium or Cetyltrimethylammonium bromide, be added silicon source amount and amphiphilic cationic surfactant additive amount
Molar ratio is between 10~30.
Preferably, roasting condition described in step (5) is in Muffle furnace in 550 DEG C of roasting 6h.
Using above-mentioned technical proposal, the invention has the benefit that the advantage of the invention is that with pair cheap and easy to get
Parent's property cationic surfactant is as structure directing agent (being denoted as SDA), and under conventional hydrothermal synthesis condition, nanometer is made in a step
The porous grade ZSM-5 molecular sieve of lamellar structure.The ZSM-5 molecular sieve for using the method for the invention to prepare is high-crystallinity by thickness
The lamellar structure in tufted aggregation that degree is 30~50nm.Preparation method provided by the invention simplifies existing preparation nanometer sheet
The step of layer structural porous grade ZSM-5 molecular sieve, expensive structure directing agent is not needed, preparation cost is reduced.This system
Preparation Method has the advantages that crystallinity is high, yield is high, operating procedure is simple and is easily isolated.
In addition, the molecular sieve is that interaction between amphiphilic cationic surfactant and inorganic species freely assembles
Made of the ZSM-5 molecular sieve with lamellar structure, there is biggish specific surface area, shorter diffusion path and preferable stablize
Property is serially connected perforation between the multistage hole of ZSM-5 molecular sieve, can give full play to their mutual diffusion features, be used for
Catalysis reaction.
Detailed description of the invention
Fig. 1 is the .X ray powder diffraction (XRD) for the porous grade ZSM-5 molecular sieve of nano-lamellar structure that embodiment 1 synthesizes
Spectrogram.
Fig. 2 is stereoscan photograph (SEM) figure for the porous grade ZSM-5 molecular sieve of nano-lamellar structure that embodiment 1 synthesizes.
Fig. 3 is transmission electron microscope photo (TEM) figure for the porous grade ZSM-5 molecular sieve of nano-lamellar structure that embodiment 1 synthesizes.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
Illustrate first, in the examples below:
The XRD analysis of sample uses Rigaku company D/MAX2200 type X-ray powder diffraction instrument.Test condition are as follows:
Cu target, K α radiation, Ni filtering, tube voltage 40Kv, tube current 30mA, 5 ° -50 ° of scanning range (2 θ), scanning speed are 4 °/min,
0.02 ° of step-length；
The SEM measurement of sample is tested using Hitachi, Japan S4800 type field emission scanning electron microscope, all samples
It is handled before testing by metal spraying；
The TEM of sample measures FEI Co. of U.S. TecnaiG20 type transmission electron microscope, and operation voltage is 200KV.
The present invention is described further for the following examples, but is not intended to limit the present invention.
Embodiment 1
(1) potassium hydroxide (0.939g) is dissolved in wiring solution-forming A in 36.166g deionized water, by load weighted isopropanol
Aluminium (0.274g) is added in the solution A of part (40% of gross mass) stirring 2h and forms solution B；
(2) suitable ethyl orthosilicate (5.58g) is slowly dropped in the solution A of part (30% of gross mass) stirring 2h
Form solution C；
(3) B is added in C and stirs 5h formation solution D；
(4) cetyl trimethylammonium bromide (0.488g) is added in the solution A of part (the 30% of gross mass), is stirred
After 1~3h, it is added in solution D and continues to stir 1h formation reaction mixture, the hydrothermal crystallizing 15d at 175 DEG C；
(5) after reaction, take out sample, a large amount of water rinse after in 120 DEG C of drying overnight, then in Muffle furnace
550 DEG C roast 6 hours.It can be obtained the porous grade ZSM-5 molecular sieve of nano-lamellar structure.
XRD, SEM, tem analysis are carried out to the porous grade ZSM-5 molecular sieve of nano-lamellar structure that embodiment 1 is prepared,
X-ray diffraction characterization is as shown in Figure 1, scanning electron microscope characterizes as shown in Fig. 2, transmission electron microscope characterization is as shown in Figure 3, it will thus be seen that
It will be seen from figure 1 that there is one group of double peak between 2 θ=7~9 °, occur Five Fingers Peak, 2 θ=44 between 2 θ=22~25 °
~46 ° have one group of double cutting edge of a knife or a sword, meet MFI structure feature, and occur without miscellaneous peak, show that the sample synthesized is ZSM-5 molecular sieve；
It can directly be obtained from Fig. 2, molecular sieve is to be accumulated by the nanoscale twins with a thickness of 30~50nm in tufted；As shown in figure 3, receiving
The superposition high-sequential of rice piece, lamellar structure are overlapped mutually each along b axis direction, as can be seen from the figure apparent diffraction lattice
Striped shows that the basic unit for constituting lamellar structure all has the essential rather than unformed silicon of crystal.
Embodiment 2
(1) potassium hydroxide (0.939g) is dissolved in wiring solution-forming A in 36.166g deionized water, intends thin water for load weighted
Aluminium stone (0.247g) is added in the solution A of part (40% of gross mass) stirring 4h and forms solution B；
(2) suitable ethyl orthosilicate (5.58g) is slowly dropped in the solution A of part (30% of gross mass) stirring 2h
Form solution C；
(3) B is added in C and stirs 5h formation solution D；
(4) cetyl trimethylammonium bromide (0.488g) is added in the solution A of part (the 30% of gross mass), is stirred
2h is then added in solution D and continues to stir 1h formation reaction mixture, the hydrothermal crystallizing 15d at 175 DEG C；
(5) after reaction, take out sample, a large amount of water rinse after in 120 DEG C of drying overnight, then in Muffle furnace
550 DEG C roast 6 hours.It can be obtained the porous grade ZSM-5 molecular sieve of nano-lamellar structure.
Embodiment 3
(1) potassium hydroxide (0.939g) is dissolved in wiring solution-forming A in 36.166g deionized water, by load weighted aluminium powder
(0.147g) is added in the solution A of part (40% of gross mass) stirring 2h and forms solution B；
(2) suitable ethyl orthosilicate (5.58g) is slowly dropped in the solution A of part (30% of gross mass) stirring 3h
Form solution C；
(3) B is added in C and stirs 5h formation solution D；
(4) cetyl trimethylammonium bromide (0.488g) is added in the solution A of part (the 30% of gross mass), is stirred
2h is then added in solution D and continues to stir 1h formation reaction mixture, the hydrothermal crystallizing 15d at 175 DEG C；
(5) after reaction, take out sample, a large amount of water rinse after in 120 DEG C of drying overnight, then in Muffle furnace
550 DEG C roast 6 hours.It can be obtained the porous grade ZSM-5 molecular sieve of nano-lamellar structure.
Embodiment 4
(1) sodium hydroxide (0.939g) is dissolved in wiring solution-forming A in 36.166g deionized water, by load weighted isopropanol
Aluminium (0.274g) is added in the solution A of part (40% of gross mass) stirring 3h and forms solution B；
(2) suitable ethyl orthosilicate (5.58g) is slowly dropped in the solution A of part (30% of gross mass) stirring 4h
Form solution C；
(3) B is added in C and stirs 5h formation solution D；
(4) cetyl trimethylammonium bromide (0.488g) is added in the solution A of part (the 30% of gross mass), is stirred
3h is then added in solution D and continues to stir 1h formation reaction mixture, the hydrothermal crystallizing 15d at 175 DEG C；
(5) after reaction, take out sample, a large amount of water rinse after in 120 DEG C of drying overnight, then in Muffle furnace
550 DEG C roast 6 hours.It can be obtained the porous grade ZSM-5 molecular sieve of nano-lamellar structure.
Embodiment 5
(1) potassium hydroxide (0.939g) is dissolved in wiring solution-forming A in 36.166g deionized water, by load weighted isopropanol
Aluminium (0.274g) is added in the solution A of part (40% of gross mass) stirring 2h and forms solution B；
(2) suitable ethyl orthosilicate (5.58g) is slowly dropped in the solution A of part (30% of gross mass) stirring 2h
Form solution C；
(3) B is added in C and stirs 2h formation solution D；
(4) dodecyl trimethyl ammonium bromide (0.413g) is added in the solution A of part (the 30% of gross mass), is stirred
1h is then added in solution D and continues to stir 1h formation reaction mixture, the hydrothermal crystallizing 15d at 175 DEG C；
(5) after reaction, take out sample, a large amount of water rinse after in 120 DEG C of drying overnight, then in Muffle furnace
500 DEG C roast 5 hours.It can be obtained the porous grade ZSM-5 molecular sieve of nano-lamellar structure.
Embodiment 6
(1) potassium hydroxide (0.939g) is dissolved in wiring solution-forming A in 36.166g deionized water, by load weighted isopropanol
Aluminium (0.274g) is added in the solution A of part (40% of gross mass) stirring 2h and forms solution B；
(2) suitable ethyl orthosilicate (5.58g) is slowly dropped in the solution A of part (30% of gross mass) stirring 2h
Form solution C；
(3) B is added in C and stirs 7h formation solution D；
(4) Cetyltrimethylammonium bromide (0.526g) is added in the solution A of part (the 30% of gross mass), is stirred
2h is then added in solution D and continues to stir 1h formation reaction mixture, the hydrothermal crystallizing 8d at 175 DEG C；
(5) after reaction, take out sample, a large amount of water rinse after in 100 DEG C of drying overnight, then in Muffle furnace
600 DEG C roast 6 hours.It can be obtained the porous grade ZSM-5 molecular sieve of nano-lamellar structure.
Embodiment 7
(1) potassium hydroxide (0.939g) is dissolved in wiring solution-forming A in 36.166g deionized water, by load weighted isopropanol
Aluminium (0.274g) is added in the solution A of part (40% of gross mass) stirring 2h and forms solution B；
(2) suitable white carbon black (5.584g) is slowly added into the solution A of part (30% of gross mass) stirring 2h shape
At solution C；
(3) B is added in C and stirs 5h formation solution D；
(4) cetyl trimethylammonium bromide (0.488g) is added in the solution A of part (the 30% of gross mass), is stirred
After uniformly, it is added in solution D and continues to stir 1h formation reaction mixture, the hydrothermal crystallizing 18d at 170 DEG C；
(5) after reaction, take out sample, a large amount of water rinse after in 120 DEG C of drying overnight, then in Muffle furnace
500 DEG C roast 6 hours.It can be obtained the porous grade ZSM-5 molecular sieve of nano-lamellar structure.
Embodiment 8
(1) potassium hydroxide (0.939g) is dissolved in wiring solution-forming A in 36.166g deionized water, by load weighted isopropanol
Aluminium (0.274g) is added in the solution A of part (40% of gross mass) stirring 2h and forms solution B；
(2) suitable silica solution (5.590g) is slowly dropped in the solution A of part (30% of gross mass) stirring 2h shape
At solution C；
(3) B is added in C and stirs 3h formation solution D；
(4) cetyl trimethylammonium bromide (0.488g) is added in the solution A of part (the 30% of gross mass), is stirred
After uniformly, it is added in solution D and continues to stir 1h formation reaction mixture, the hydrothermal crystallizing 10d at 180 DEG C；
(5) after reaction, sample is taken out, a large amount of water are dried after rinsing in 90 DEG C overnight, then 600 in Muffle furnace
DEG C roasting 4.5 hours.It can be obtained the porous grade ZSM-5 molecular sieve of nano-lamellar structure.
It should be noted that the present invention, in sieve synthesis procedure, without adding crystal seed Gel Precursor, there are no need to make
With two kinds of organic formwork agents, process is simple, reduces cost of material, only needs a kind of cationic surface in synthesis process of the present invention
Activating agent, so that it may synthesize the porous grade ZSM-5 molecular sieve catalyst of nano-lamellar structure, simplify synthesis technology, reduce original
Expect cost.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (8)
1. nano-lamellar structure multi-stage porous ZSM-5 molecular sieve, which is characterized in that the molecular sieve has nano-lamellar structure, institute
Molecular sieve is stated by accumulating with a thickness of 30~50nm nanoscale twins in tufted, the molecular sieve passes through with amphiphilic cation form
Face activating agent is structure directing agent, is made in next step in conventional hydrothermal synthesis condition.
2. the synthetic method of nano-lamellar structure multi-stage porous ZSM-5 molecular sieve as described in claim 1, which is characterized in that packet
Include following steps:
(1) alkali source is dissolved in wiring solution-forming A in deionized water, by load weighted silicon source be added in 40% solution A stirring 1~
5h forms solution B；
(2) suitable silicon source is added in 30% solution A and stirs 2~5h formation solution C；
(3) 2~8h is mixed in solution B and solution C and forms solution D；
(4) by suitable amphiphilic cationic surfactant, it is added to 1~3h of stirring in 30% solution A, is then added to
Continue 1~4h of stirring in solution D and forms reaction mixture, 7~18d of hydrothermal crystallizing at 170~180 DEG C；
(5) after reaction, take out sample, a large amount of water rinse after in 80~120 DEG C of drying overnight, then in Muffle furnace
500~600 DEG C of 4~6h of roasting.
3. nano-lamellar structure multi-stage porous ZSM-5 molecular sieve synthetic method as claimed in claim 2, which is characterized in that step
(1) alkali source described in is potassium hydroxide or sodium hydroxide.
4. nano-lamellar structure multi-stage porous ZSM-5 molecular sieve synthetic method as claimed in claim 2, which is characterized in that step
(1) silicon source described in is aluminium isopropoxide, boehmite or aluminium powder.
5. nano-lamellar structure multi-stage porous ZSM-5 molecular sieve synthetic method as claimed in claim 2, which is characterized in that step
(2) silicon source described in is ethyl orthosilicate, white carbon black or silica solution.
6. the synthetic method of nano-lamellar structure multi-stage porous ZSM-5 molecular sieve as claimed in claim 2, which is characterized in that step
Suddenly the mol ratio of reaction mixture described in (4) are as follows: 20-50 SiO2∶0.3-2 Al2O3∶20-30 ROH∶1000-3000
H2O: 1-10 SDA, ROH therein are expressed as NaOH or KOH.
7. nano-lamellar structure multi-stage porous ZSM-5 molecular sieve synthetic method as claimed in claim 2, which is characterized in that step
(4) amphiphilic cationic surfactant described in be dodecyl trimethyl ammonium bromide, cetyl trimethylammonium bromide or
Cetyltrimethylammonium bromide, the molar ratio of amount and amphiphilic cationic surfactant additive amount that silicon source is added 10~
Between 30.
8. nano-lamellar structure multi-stage porous ZSM-5 molecular sieve synthetic method as claimed in claim 2, which is characterized in that step
(5) roasting condition described in is in Muffle furnace in 550 DEG C of roasting 6h.
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| CN107128947A (en) * | 2017-06-30 | 2017-09-05 | 华南理工大学 | A kind of preparation method of the middle zeolite molecular sieves of micro-diplopore ZSM 5 |
| CN108455626B (en) * | 2018-05-28 | 2019-10-29 | 西北大学 | The ZSM-5 multistage porous molecular sieve and preparation method thereof of block ZSM-5/ nanoscale twins composite construction |
| CN108975351B (en) * | 2018-08-02 | 2021-07-02 | 太原理工大学 | Preparation method of hierarchical pore ZSM-5 zeolite microspheres |
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| CN112279268A (en) * | 2020-08-06 | 2021-01-29 | 中国石油大学胜利学院 | Preparation method and application of hierarchical pore ZSM-5 nano lamellar zeolite |
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